有機(jī)硅電解液：安全性和高電壓性能研究進(jìn)展(已修改)
2025-03-02 13:27 本頁(yè)面
【正文】 有機(jī)硅電解液：安全性和高電壓性 能研究進(jìn)展 Background ? Safety issues related with Liion Batteries ? Safe electrolytes for highvoltage batteries Organosilicon based electrolytes ? Highvoltage OSbased electrolytes ? OSbased electrolytes for Si anodes Summary Outline Safety issues of LIBs: High flammability of carbonate electrolytes! LiFePO4 battery Not safe enough！ Safety of LithiumIon Batteries Safety (abuse tolerance): ? When overcharged, thermal runaway leads to fires etc. ? Runaway reaction caused by release of oxygen from cathode materials (., LiCoO2). The development of new Safe electrolyte materials! O O O R R DMC: R=CH3 DEC: R=CH2CH3 O O EC O HighVoltage CathodeMaterials Discharge potential(V) Redoxcouple Theoretical Capacity(mAh/g) Potential Range(V) LiCoPo4 2+/3+ Co 167 – LiNiPo4 ～ 2+/3+ Ni 167 – Li3V2(PO4)3 LiMPO4 3+/4+/5+ V 197 – Li2CoP2O7 2+/3+ Co b 109 – Li2MnP2O7 2+/3+ Mn b 110 – Li2NiPO4F ～ 2+/3+ Ni b 143 – LiNiSO4F C – 2+/3+ Ni 149 — Li2NiSiO4LiNiMn C O4 2+/3+ Ni b 163 — 2+/3+/4+ Ni 147 – 3+/4+3+/4+ Fe,Mn 148 – xLi2MnO3(1x)LiMeO2 (0X1,Me=Ni,Co,Mn) 2+/3+/4+3+/4 Ni,Co 3+/4+ Mn d ～ 314 – Es= Qcapacity * Vvoltage 1. Safety! 2. Highvoltage Stability! J. Power Sources, 237 (2023) 229. Highvoltage cathodes require patible electrolytes Electrolyte Challenges: N S Additives Dinitriles Ionic liquids Sulfone Fluorinated solvent Inanic pounds Sulfonate esters Carboxyl anhydrides Phosphides C C N N n O F C O O O O O CF3 F F CF3 R4 N+ R2 O C F R1 O F R1 N+ R2 O C F F F R1 N+ R2 R3 O S F O O S S O O O O S O O O O S O O O O S O O S O CF3 CF3 F3C F3C F3C CF3 O P O O O O O B O O O O O Li B O O O O F F Li Electrolyte solvents and additives for highvoltage Solvents LiBOB LiODFB C N H H C n C N , , 1/12 C J Electrochem Soc, 156 (2023)A60.。 159 (2023)A370。 160 (2023)A838. J Power Sources, 189 (2023) 576. Aprotic aliphatic dinitrile solvents n=3ADN, n=5 PMN n=6 SUN, n=8 SEN Advantages: Electrochemical window (78V) Flash point (110 ℃ , 163 ℃ forADN) Dielectric constant (2030, 55 for SCN) Disadvantages: Poor patibility with graphite Poor solubility of LiPF6 ? LiTFSI (V V, corrodes collector) ? LiBF4 (inferior ability, poor low temperature performance) J Electrochem Soc, 149 (2023)A920。 J Phys Chem B, 115 (2023) 12120. Electrochem Commun, 11 (2023) 1418。 11 (2023) 1073. SulfoneBased Electrolytes ? Advantages: ?High oxidation potential ? Low flammable ? High melting point。 Poor patibility with graphite。 Wetting problem with separator Li4Ti5O12/1M LiPF6FEC/DMC/D2 3/4/3/ (Data from ANL, USA) O F Rf1 Rf2 O D2 O FEC 1 C at 55 oC Fluorinated Based Electrolytes Advantages: ? High oxidative stability ? High flash point/low flammability (Safe) ? Compatible with graphite O Disadvantages: ? Bad performance at elevated temperatures (FEC) ? Harsh synthesis conditions/high cost 1M LiPF6 EC/DEC (3/7) 1M LiPF6 EC/DMC/MFA (3/3/4) F O H C C O CH3 F MFA 1M LiPF6 MFA LiCo2/ Graphite cell (1 Ah cell)。 Daikin data (Japan) Fluorinated Based Electrolytes Energy Environmental Science, 6 (2023) 1806。 Electrochem Commun, 10 (2023) 783. ?High ? Low flammability ? High oxidation resistance ? High viscosity (low conductivity rate capability) ? Poor wetting ?High cost J Power Sources, 189 (2023) 331。 225 (2023) 113。 233 (2023) 115. Mix with carbonate or other cosolvent performance ? Ionic Liquid Electrolytes thermal stability ? Very low rotation barrier around SiO axis, (ca. KJ/mol) ? low linear isation energy of the SiOSi angle (~ kJ/mol). Organosilicon (OS) Electrolytes: ?High ionic conductivity ? Nonflammability: Biopatible ? Excellent wetting capability ? Wide liquid phase range (40–200 oC) ? Low viscosity parable with alkylcarbonates ? Medium wide electrochemical window ? Very low glass transition temperature ? good thermal stability Alternative: Organosilicon Electrolytes O O O O O R2 R2 R1R1= H, CH3 R2= CH3, CH3CH2 Carbonate electrolytes Highly flammable! O J. Mater. Chem., 2023, 18(31), 371317。 2023, 20, 822426. Chem. Mater. , 2023, 19, 57345741. Implant neuro stimulator micro cell ( ? mm2, ? 1g) Organosilicon as Safe Electrolytes 1. Excellent cyclability； 2. Electrochemically s
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